JPS60249148A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a color photographic sensitive material superior in storage stability, and image quality, such as sharpness, graininess, and color reproducibility, and high in ensitivity by incorporating couplers or hydroquinones capable of cleaving a photographic useful group by reaction with the oxidation product of a developing essential agent. CONSTITUTION:A compd. represented by general formula ( I a) (W and Z are each O, S, or >N-X5; each of X1-X5 is H or an org. residue; PUG is a photographic useful group; and A is a residue of couplers of hydroquinones, preferably, a coupler residue) reacts with the oxidation product of said developing agent and releases the following compd. (a). It diffuses through an emulsion, and passes through the reaction course as shown in the scheme, resulting in producing the PUG. The reaction velocity of each stage can be optionally controlled by selecting W, Z, X1, X2, X3, and X4 properly. Also the diffusion velocity of the compds. of (a), (b), and (c) through the emulsion can be optionally controlled.

Description

[Detailed description of the invention]

(Field of Application of the Invention) The present invention relates to a color photographic light-sensitive material containing a novel compound capable of making photographically useful groups available during the processing of an image. (Prior art) By color-developing a silver halide photographic material, the oxidized aromatic-amine color developing agent and coupler react to form indophenol, indoaniline,
Indamine, azomethine. It is known that phenoxazine, phenazine and similar dyes can be produced to form one color images. In this method, a subtractive color method is usually used for color reproduction, such as back, green,
A silver halide emulsion that is selectively sensitive to red and yellow, magenta, and cyan color image forming agents that are in a complementary color relationship, respectively, are used. To form a yellow image, for example, an acylacetanilide or dianzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indacylon coupler is mainly used. , primarily phenolic couplers such as phenols and naphthols are used to form cyan images. It has been known that couplers are used not only to form dye images but also to release photographically useful groups. For example, U.S. Patent No. 3.2
27. jJrII No. 3. /at, o62 and J
our own of the American Che
Mical 5ociety Volume 7λ (/10 years)
Couplers that release development inhibitors or dyes upon coupling are described, such as on page 1333. Also, US Patent No. 3.70! No. t, No. 10/ discloses couplers that are capable of releasing bleach inhibitors from the coupling site after reaction of the coupler with oxidized developing agent. More recently, Japanese published patent j7-7101≠j
No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, discloses couplers that release a fogging agent from the coupling site after fVE of the oxidized developing agent and the coupler. Compounds that do not produce dyes but release photographically useful groups by reacting with oxidized developing agents have also been known. For example, US Pat. No. 3,230rt3 discloses hydroquinone which releases a development inhibitor. As is well known from the above-mentioned specifications, compounds that release photographically useful groups can improve color reproducibility, improve graininess, and improve graininess.
It is used for purposes such as improving sharpness or increasing sensitivity. It is common knowledge in the art that for compounds that release photographically useful groups, techniques for adjusting the speed at which they are released and the extent to which they are diffused into emulsions are more important than adjusting the photographic action of the photographically useful groups. . It is also known that the greater the dispersibility of the released development inhibitor, the greater the sharpness.
-/4At7/λ. One such technique is U.S. Patent No. 24A1. 6λ, same≠
Examples of couplers having timing groups have been proposed in , Hiroo et al., No. 3.23. These known couplers include couplers in which a photographically useful group is directly bonded to the coupler (
For example, U.S. Patent No. 3.227. ! The coupling speed is increased compared to the coupler exemplified in No. J, and it has a certain degree of performance. However, the degree of diffusion of photographically useful groups into the emulsion was small, and the photographic performance still needed improvement. Furthermore, known couplers having a timing group have problems with stability during film storage after being coated on a film, and have drawbacks such as complete loss of functionality due to decomposition, desensitization, and increase in coupler size. (Objective of the Invention) The compound of the present invention improves the above-mentioned drawbacks and has further excellent photographic properties. In other words, the object of the present invention is to develop a novel material that is chemically stable and capable of releasing photographically useful groups at a desired rate, and that has a high diffusivity of the released photographically useful groups and can effectively control its range of action. By using compounds,
Excellent storage stability. Sharpness: 1 Excellent image quality including graininess and color reproducibility. The object of the present invention is to provide a highly sensitive color photographic material. (Structure of the Invention) These objects of the present invention have been achieved by a silver halide color photographic light-sensitive material containing all compounds capable of cleaving a group represented by the following general formula (T) by reaction with an oxidized developing agent. General formula (I) In the formula, W and Z each represent an oxygen atom, a sulfur atom, or -N-, and xl, x2. x3゜X4 and Xs each represent a hydrogen atom or an organic residue, PU
G represents a photographically useful group, n represents/or 2,
xl, x2. Any two of x3, X4°Xs and PUG may be connected as divalent groups to form a ring structure. When n is 2, λ Z, J Xs and λ X
4 may be the same or different. (Description of the Invention) The compound of the present invention releases the following compound (a) t= upon reaction with an oxidized developing agent. Compound (a) diffuses in the emulsion and undergoes the reaction shown in the scheme below, eventually producing PUG. X 4 X 4 Generates a sexually useful group (PUG). The reaction rate of each step is w, z, Xi, x2. It can be arbitrarily adjusted by selecting X, 3 and X4. Furthermore, the diffusion speed of the compounds (aL (b) and (C) in the emulsion can also be adjusted arbitrarily by selecting W, Z, Xl, X2. This is done by selecting whether the compound is donative or electron-withdrawing, or hydrophilic or hydrophobic.The reason why the compound of the present invention is excellent in photographic performance is as follows.General reaction rate In theoretical discussions, it is known that in multi-step reactions there is an induction period in the rate of production of the final product.This induction period is not seen in one-step reactions and becomes more pronounced as the number of reaction steps increases. The reason why the period appears is derived from kinetic analysis, but it is a natural result because intermediates intervene in the middle.Here, when the final product (PUG) is produced in the same amount in the same reaction time, A comparison between a one-step reaction and a two-step, three-step reaction shows the following.In other words, in a one-step reaction, a large amount of PUG is produced at the beginning of the reaction.
! In contrast, in a two-step or three-step reaction, PUG is generated at the start of the reaction.
The amount produced is small, but after a certain induction period, the amount produced rapidly increases. It is believed that this precisely explains the excellent performance of the compounds of the present invention. That is, the compound released from the compound of the present invention diffuses through the emulsion without immediately producing PUG, and after an induction period, it rapidly becomes PUG.
Generate G. This not only increases the spreadability of PUG, but also increases the
This means that K effectively controls the range of action of G. Couplers or hydroquinones are capable of cleaving the group represented by the general formula (T) by reaction with an oxidized developing agent. For couplers. Although it is preferable that the group of general formula (I) is bonded to the coupling position, all cases where it is detached from the coupler as a result of the coupling reaction are included. For example, when the coupler is connected to the mother nucleus, the example described in JP-A No. 7 μO, Shojl-, 2009, can be used. This also includes cases where the bond is not directly bonded to the coupling position but via a timing group. Such examples include, for example, U.S. Pat.
, 2 Guza, Ri A, No. 2, Same≠, Gu 09,323, British Patent No. 4,713, Japanese Published Patent No. 37-
661.37/issue, same j7-/za1.03j, same 3l
-41r, No. 721, same! l-209゜737, N5
1-. 209.731Ji+, same jl-207,73?
This is the timing group described in No. moreover,
In the case of couplers, cases in which they are emitted from bis-type couplers, polymer couplers, etc. are also covered by this patent. A preferred compound used in the present invention is represented by the following general formula (Ia). General formula (Ia) where W, Z, Xl, X2. X3. X4. n and P.U.
G represents the same meaning as defined in general formula (T). In general formula (Ia), A is a coupler residue or a hydroquinone, and a preferable group represented by A is a coupler residue. When A represents a yellow image-forming coupler residue, it is preferably of the piparoylacetanilide type, benzoylacetanilide type, or malondiester type. malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type,
Benzothiazolylacetate type, indoxazinolacetamide type, benzoxacylylacetate type, benzimidazolylacetamide type or indimidazolylacetate type coupler residue, US patent! , 141
/, coupler residues derived from heterocyclic-substituted acetamides or heterocyclic-substituted acetates contained in IIO, or U.S. Pat. No. 3,770,4 (!J, British Pat.
, Gujri, No. 71, West German patent (OLS). 103.0 Tata No. 1 Japanese Published Patent jO-/3ri. 7.31j or Research Disclosure-1j
Coupler residues derived from acylacetamides described in No. 737 or US Patent a, O≠B. ! Examples include the heterocyclic coupler residue described in No. 74L. When A represents all magenta image-forming coupler residues, it is preferably of the j-oxocopyrazoline type. Virazoloindimidazole type. Pyrazolotriazole type, cyanoacetophenone type, pyrazoloimidazole type or OLS No. 3, /λ/, 55
Examples include N-heterocycle-substituted acylacetamide type coupler residues described in No. When A represents a cyan image-forming coupler residue, it preferably includes a coupler residue having a phenol nucleus or an α-naphthol nucleus. When A represents all the coupler residues that do not substantially form a dye, examples of this type of coupler residues include indanone type and acetophenone type coupler residues, and specifically, U.S. Patent μ, 0! J,, No. 273, same +, ore
, +y1 No. 3, 1, 3.2゜3μj, No. 3. Rij
♂, Tata No. 3, same 3. ri61, rijri number, same≠, O≠t
, No. 37≠, or No. 3, 23g, Tata No. 6, etc. In general formula (Ia), the group represented by PUG is specifically a development inhibitor, a development accelerator, and a fogging agent. Examples include dyes, additives, couplers, desilvering promoters, silver halide solvents, competing compounds or desilvering inhibitors. These compounds can be selected depending on the purpose. Further, photographic effects can be achieved by adjusting the speed to a desired level depending on the purpose. Furthermore, the photographic effect of PUG can be adjusted to desired properties depending on the purpose. It involves adjusting the substituents of PUG, such as adjusting whether it is electron-withdrawing or electron-donating;
Alternatively, it can be carried out by adjusting whether it is hydrophilic or hydrophobic. Preferred examples of PUG include the following. General formula (P-/) General formula (P-,2) -General formula CP-3> 2 General formula (P--t) General formula (P-6) General formula (P-7) 4 General formula (P -4) General formula (P-ta) In the formula, G1 is a hydrogen atom, a halogen atom, an alkyl group (e.g. methyl group, ethyl group, etc.), an acylamino group (e.g. benzamide group, hexane amide group), an alkoxy group (e.g. butoxy group, benzyloxy group), sulfonamide group (e.g. octane sulfonamide group, Alkylamino groups (cyclohexylamino groups, etc.), anilino groups (anilino groups, 4!-methoxycarbonylanilino groups, etc.), amino groups, alkoxycarbonyl groups (methoxycarbonyl groups,
butoxycarbonyl group (1, etc.), acyloxy group (acetyl group, dutanoyl group, benzoyl group, etc.), nitro group,
Cyano group. Sulfonyl group (phthanesulfonyl group, benzenesphonyl group, etc.), aryloxy group (phenoquino group, naphthyloxy group, etc.), hydroxy group. Neoamide group (butanethioamide group, benzenethiocarbonabado group, etc.), carbamoyl group (carbamoyl-
JE', N-arylcarbamoyl group nato). Sulfamoyl group (sulfamoyl group, N-sulfamoyl group, etc.), carboxy f group, ureido group (
ureido group, N-ethylureido group, etc.) or aryloxycarzenyl group (phenoxycarbonyl group%≠
-methoxyphenoxycarbonyl group, etc.). In the formula, G2 is a hydrogen atom, an alkyl group (for example, a methyl group,
ethyl group) or aryl group (e.g. phenyl group,
(naphthyl group). In the formula, G3 hydroxy group, sulfonamide group (e.g. butanesulfonamide group, benzenesulfonamide group)
, represents an amino group, an alkylamine group (e.g. ethylamino group, cyclohexylamino group), anilino group (e.g. anilino group, goomethylanilino group) or a hydrogen atom, and represents the 03 of the λ of the general formula (P, t). may be the same or different, provided that both are not hydrogen atoms. In general formulas (PA) and (P-7), G4 represents an aryl group (eg, phenyl group, naphthyl group). Furthermore, KO2 is a hydrogen atom, a heterocyclic thio group (e.g., a group represented by the general formula (P-3> or (P-da)), or a nitrogen-containing heterocyclic group fused to a benzene ring (e.g., a group represented by the general formula (P-3)). /) or (P-2)). f represents an integer of l or λ. In the formula, ■1 is a nitrogen atom or -(ni group (G 11 has the same meaning as already explained) (which may be the same or different from other 01 present in the molecule).In the formula, v2 represents an oxygen atom, a sulfur atom, or 2).In the general formula (P-≠) When vl is 10 = group Table 1, the two 01 groups are connected to form a benzene-fused ring (for example, when V2 is -NH-, it becomes a benzimidazolylthio group, and when 2 is an oxygen atom, it becomes a benzoxazino group). (becomes a ruthio group). General formula (P-/), (P-2), (P-J). (P-4'), (P-zL (P-t), ( P-7). G1.G2゜G3 in (P-♂) and (P-ta)
．． G4 or G5 contains an alkyl group moiety. When the alkyl group has carbon atoms /, 2, preferably /, 1
It may be 0 substituted or unsubstituted, linear or branched, linear or cyclic, saturated or unsaturated. Furthermore, G1. G2. When G3゜G4 or G5 contains an aryl group moiety, the aryl group has 6 to io carbon atoms and is preferably a substituted or unsubstituted phenyl group. General formulas (P-/), (P-2), (P-J) and (P
-1 is a development inhibitor. These groups have the general formula (1
), when A represents all coupler residues, generally D
It is called an IR coupler. Compared with known DIR couplers, the JDIR couplers of the present invention could more effectively control the entire range of action of the inhibitor and had sufficient stability. As a result, a color photographic image with good color reproducibility due to single-graininess and single-layer effect and especially good sharpness was obtained. The general formulas (P-1, (P-+) and (P-7>) are developing agents and have a reducing action. Various effects of these groups on photographic properties are known. When reducing oxidized developing agent, it is called a competitive compound and is good for improving graininess or sharpness, and when reducing silver halide or acting as an auxiliary developer, it increases sensitivity. The general formulas (P-za) and (P-ta) are examples of couplers.These compounds functioned as competitive couplers and were particularly excellent in improving grain size.General formulas (P-j) and (P-f ) and (P-ta), when G5 is a development inhibitor such as a heterocyclic thio group, an inhibitory effect is further added, so the function as a DIR coupler can be efficiently added. General formula (Ia ), Xi, x2.Xa and X4
When represents an organic residue, it is preferably one listed below: alkyl group, aryl group. Acyl groups (eg acetyl, indiyl). Sulfonyl group (eg, t is methanesulfonyl group, inzenesulfonyl group) s Carbamoyl group C example, t is ethylcarbamoyl group, phenylcarbamoyl group). Sulfamoyl group (e.g. ethylsulfamoyl group, phenylsulfamoyl group), alkoxycarbonyl group (
For example, ethoxycarbonyl group, butoxycarbonyl group)
, an alkoxysulfonyl group (e.g. phenoxycarbonyl group 1 μm methylphenoxycarbonyl group), an alkoxysulfonyl group (e.g. a methoxysulfonyl group, an ethoxysulfonyl group), an anoroxysulfonyl group (
For example, a phenoxysulfonyl group, a methoxyphenoxysulfonyl group), a cyan group, a nitro group, a nitroso group, a carboxyl group, a sulfo group, a thioacyl group (for example, a thioacetyl group, a thiobenzoyl group). It is a thiocarbamoyl group (ethylthiocarbamoyl group) or an imidoyl group (for example, N-ethylimidoy) n group). When these substituents contain an alkyl group moiety, the alkyl group has a carbon number of l-λθ, preferably 1 to IO, substituted or unsubstituted, linear or branched, chain or cyclic, saturated or unsaturated. In any case, the aryl group is a phenyl group or a naphthyl group, preferably a substituted or unsubstituted phenyl group. In the general formula (Ta), W and Z are ax ゛-N-? When represented, X5Fi hydrogen atom or the above X1. X2. X3. Selected from the organic residues listed for X4. Xi, x2, x3. Any two of x and X5 may form a divalent group and connect to form a ring structure. Examples of preferred ring structures are as follows. In the example below, the bond indicated by a star (*) represents the position where it bonds with A.
The bond indicated by **) represents the position where it is bonded to PUG. 4 , .-Y 4 to Y-' 4 where WsZ, Xl, X2. X3. X4 has the general formula (Ia
), and Y represents a divalent organic residue for forming a ≠-membered ring to a 6-membered ring, and is preferably the following. 8 In the formula, X6, X7 and X8 are each a hydrogen atom or the above xl, X2. It is selected from the organic residues mentioned in Xa, X4 and X5. -Furthermore, the present invention is particularly effective because of the general formula (
■ In a), A is the following general formula (■). (III), (IV), (V), (VI), (■), (
■). When it is a coupler residue represented by (IX), (X), (XI) or (■). These couplers are preferred because of their high coupling speed. General formula (U) General formula (III) General formula (■) 5 General formula (V) General formula (Vl) General formula (■) General formula (vIll) General formula (IX) General formula (X) General formula (XI ) General formula (■) R1, -CH-R,. In the above formula, the free bond derived from the coupling position eliminates the bonding position of the coupling-off group. In the above formula, R1, R2, Ra, Ra. When R5, Rs, R7, R8, R9, R1o or R11 contains a diffusion-resistant group, it has a total number of carbon atoms of r to 32.
Preferably, the carbon number is selected such that io-co.lambda., and in other cases, the total number of carbon atoms is preferably lj or less. Next, R1-R11°1, m of the general formulas (n) to (■)
and p will be explained. In the formula, R1 represents an aliphatic group, an aromatic group, alkoxy #E or a heterocyclic group 't, Rz and R3 each represent an aromatic monogroup or a heterocyclic group. In the formula, the aliphatic group represented by R1 preferably has a hard number l
-Coλ may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amine group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R1 are: inpropyl, inbutyl, tert-dityl, isoamyl. tert-amyl group, /,! -dimethylbutyl group. t, t-)) tylhexyl M, t+7-dinitylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group,
Cophenoxyisopropyl group. λ-p-tert-butylphenoxyisoprobyl group,
These include α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinibado)isopropyl group, α-(phthalimido)isopropyl group, α-(ink/sulfonamido)isopropyl group, and the like. When R1, Rzt or R3 represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted, and the aromatic group such as the phenyl group is an alkyl group having a carbon number of 3λ or less,
alkenyl group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group,
It may be substituted with an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group may have an aromatic group such as phenylene interposed in its chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having a total number of carbon atoms of /, 2.2. The phenyl group represented by R1, R2 or R3 further includes an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, including those substituted with a lower alkyl group having 1 to 6 carbon atoms. Alternatively, it may be substituted with a halogen atom. R1, R2 or R3 may represent a substituent 1 in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents. When R1 is an alkoxy group, the alkyl moiety has carbon atoms ranging from 1 to 32. Preferably, it represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group of 1 to λλ, and these are a halogen atom and an aryl group. It may be substituted with an alkoxy group or the like. When R1s R2 or R3 represents a heterocyclic group, the heterocyclic group is connected to the carbon atom of the carbonyl group of the acyl group or the nitrogen of the amide group in alpha acylacetomide through one of the carbon atoms forming the ring, respectively. Combine with atoms. Examples of such heterocycles include thiophene, 7rane, birane, and pyrrole. Pyrazole, pyridine, pyrazine, pyrimidine. Examples include pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring. In the general formula (IV), Rs has 1 to 32 carbon atoms, preferably 2-2 linear or branched alkyl groups (e.g. methyl, impropyl, tert-dutyl, hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl group, etc.), cyclic alkyl groups (e.g. Jtil' cyclomethyl group, cyclohexyl group, etc.), aralkyl groups (e.g. Id/zyl, β-phenylethyl group, etc.) ), cyclic alkenyl & (e.g. cyclointenyl, cyclohexenyl group, etc.) 1, these are halogen atoms. Nitro group, cyano group, aryl group, alkoxy group. Aryloxy group, carboxy group, alkylthiocarbonyl group, arylthio group. Carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, teryl group Sulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group. Anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. Further, KRs may be substituted. Further, KRs may represent an aryl group (for example, a phenyl group, α- or β-naphthyl group, etc.). The aryl group may have one or more substituents, and Examples of groups include alkyl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, ffl-like alkenyl groups, halogen atoms, nitro groups, cyano groups.Aryl groups, alkoxy groups, aryloxy groups.carboxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups. group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, Dialkylamino group. Anilino group % N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. More preferred as R5 is at least the ortho position. /fli is a phenyl substituted with an alkyl group, an alkoxy group, a halogen atom, etc., and this is useful because the coupler remaining in the film does not change color due to light or heat. Furthermore, R5 is a heterocyclic group (for example, a two-membered or six-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, or a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, or a benzothiazolyl group). oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), a heterocyclic group substituted with the substituents listed for the above-mentioned aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group. Arylsulfonyl group, alkylcarbamoyl group. It may also represent a carpamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R4it hydrogen atom, carbon number 7 to 32, preferably / to 2.2 straight chain

[7 is a branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl group (these groups may have a substituent listed for R5 above), an aryl group, and a heterocyclic group (these are the same as for R5 above) may have the listed substituents), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarminyl group, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, naphthoxycarbonyl group), ). Aralkyloxycarbonyl group (e.g. benzyloxycarbonyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, heptadecyloxy group, etc.), aryloxy group (e.g. phenoxy group, tolyloxy group, etc.)
, alkylthio groups (e.g. ethylthio group, dodecylthio group, etc.), alkylthio groups (e.g. phenylthio group, α
-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, j-[:(21 μm di-tert-amylphenoxy)acetamido]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.), ureido group (e.g., ureido,
N-arylureido, N-alkylureido groups, etc.)
, urethane group. thiourethane group, tri-amino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N
-acetylanilino group, λ-chloro! -tetradecanamide anilino group, etc.), alkylamino group (e.g. n
-butylamino group, methylamino group, cyclohexylamino group, etc.). cycloamino group (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino group (e.g. ≠-pyridylamino group,
(2-inzoxazinolamino group, etc.), alkylcarbonyl group (e.g., methylcarbonyl group), arylcarbonyl group (e.g., phenylcarbonyl group, etc.), sulfonamide group (e.g., eva-alkylsulfonamide group, sulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenylcarbamoyl group), sulfamoyl group (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl group), famoyl group, N-arylsulfamoyl group, N-alkyl-N
-arylsulfamoyl group %N, N-diarylsulfamoyl group), cyano group, hydroxy group, mercapto group. 0 represents either a halogen atom or a sulfo group. In the formula, R6 is a hydrogen atom or a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or aralkyl group having a carbon number of 1 to 32, preferably 1 to 22. , or a cyclic alkenyl group. These may have the substituents listed for R5 above. Further, R6 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R above. R6 is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, or a diacylamine group. , ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group,
Alkylamino group, dialkylamino group, anilino group. N-arylanilino group, N-alkylanilino group, N
- may represent an acruanilino group, a hydroxy group or a mercapto group. R7, R8 and R9 each represent a group used in a conventional high-equivalent phenol or α-naphthol coupler; specifically, R7 includes a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon residue, N-arylureido group, acylamino group, -0
-R12 or -8-R12 (however, R12 is an aliphatic hydrocarbon residue), and when there are co or more R7s in the same molecule, two or more R7s may be different groups. , aliphatic hydrocarbon residues include those having substituents. Also, when these substituents contain an aryl group. The aryl group may have the substituents listed for R5 above. Examples of R8 and R9 include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom,
These groups also include those having substituents. Further, R8 and R9 may jointly form a nitrogen-containing heterocyclic nucleus. The aliphatic hydrocarbon residues may be either saturated or unsaturated, or straight-chain. It may be either branched or cyclic. and preferably alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, dutchyl, t-dutyl, isobutyl, dodecyl, octadecyl, cyclobutyl,
cyclohexyl, etc.), alkenyl groups (for example, allyl, octenyl, etc.). Aryl groups include phenyl groups, naphthyl groups, etc.
Representative heterocyclic residues include pyridinyl, quinolyl, chenyl, piperidyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amines, and sulfo. Examples include groups such as alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. 1 represents an integer of 1-μ; 1m represents an integer of 7 to 3; and p represents an integer of 1 to 1. Rlo is a carbonyl group, an alkanoyl group with 2 to 32 carbon atoms, preferably 2 carbon atoms, an alkanoyl group with 2 to 3 carbon atoms, preferably 2 carbon atoms, an alkanecarbamoyl group with 2 to 3 carbon atoms, preferably 2 carbon atoms, fi/~ 32 preferably represents a carbonyl group or a carbonyl group of 12. These may have a substituent, and examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, and a nitrile group. group, alkyl group or aryl group. R11 is an arylcarbonyl group, an alkanoyl group having -2 to 3λ carbon atoms, preferably 2 to 2-2 carbon atoms, an alkanoyl group having 2 to 3 carbon atoms, preferably an alkanecarbamoyl group having 2 to 220 carbon atoms, and a carbon number 1i11 (/~3λ). Preferably /N
Jλ alkoxycarbonyl group or aryloxycarmenyl group, carbon-7R number/~32 preferably lNN2
O-alkanesulfonyl group, arylsulfonyl group, aryl group, J-membered 4-6-membered heterocyclic group (hetero atom is selected from nitrogen atom, oxygen atom, sulfur atom, such as triazolyl group, imidazolyl group, Phthalimide group, succinimide group, furyl group, pyridyl group or Vi
benzotriazolyl group). These may have the substituents mentioned above for RIO. The coupler of the present invention is preferably used in combination with other conventional couplers, and has an angle of 0°/moB to the main coupler.
J Omo14b preferably t --z o mo
It is used in %. The compound of the present invention may be used in any layer such as a high-sensitivity layer, a low-sensitivity layer, or an intermediate layer depending on the purpose. Examples of the compounds used in the present invention include, but are not limited to, the following compounds. (il H (5) Cs2H,2500CCHCOOC12H25C2H5 SO2C4Hg 翰N-N The compound of the present invention can generally be synthesized by the following synthetic route. In the formula, ω represents a chlorine atom or a bromine atom. The above reaction is 1 This is usually carried out using a base.The base used is potassium hydroxide, sodium hydroxide, potassium t-butoxy, sodium methoxide, triethylamine or sodium nohydride.The reaction solvent is a polar solvent (e.g. N , N-dimethylformamide,
dimethyl sulfoxide, ethanol, etc.) or nonpolar solvents (eg, toluene, ethyl acetate, etc.). Next, a specific synthesis method for typical compounds of the present invention will be described. Synthesis Example (11) Synthesis of Exemplified Compound (1) Synthesis was performed using the following synthesis route. A methanol solution of u79 containing 2 g'% of sodium methoxide was mixed at room temperature (
λj 'C or less). into this solution. A solution of Compound-2 (7.3 g, 1 kN, dissolved in N-dimethylformamide ootyt) was added dropwise at room temperature. After reacting for 20 minutes at less than C'C, neutralize with hydrochloric acid water and convert to ethyl acetate! Extracted with 00ml. After washing with water, the oil layer was removed and dried over sodium sulfate. After half of the solvent was distilled off under reduced pressure, the precipitated crystals were taken in the mouth to obtain 33 g of compound j (i-). Step ■ 3 og of compound 3 obtained in step ■ of synthesis of exemplified compound l, and coachtradecyl. Oxyaniline (compound da) was mixed with 200 ml of λg't-NlN-dimethylformamide.To this solution was dissolved in 100 ml of N,N'-dicyclohexylcarbodiimide/2.2geN,N-dimethylformamide using JoC. The solution was added dropwise. Gradually the temperature was returned to room temperature and the reaction was allowed to proceed for 3 hours. The precipitated crystals (N,N'-dicyclohexylurea) were separated daily, ethyl acetate was added to the oral fluid, and the mixture was transferred to a separating funnel and washed with water. The oil layer was washed with water. After drying over sodium sulfate, the solvent was distilled off under reduced pressure.The residue was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain the desired coupler l as λJ.
, 4. ! I got 7. Synthesis Example (2) Exemplary Compound (Synthesis of Power) 31.0 g of Compound! (Synthesized by the method described in Japanese Published Patent No. 17-70171) and Compound O were synthesized by the following synthetic route. 22.jllfN, N-dimethylformamide, Z
Dissolved in OOllll. This solution was heated to room temperature (,2j−'
C) with t-butoxypotassium ii. Ko! ? The mixture was added in 3 portions over 30 minutes. The drained water, which had been stirred all day and night at room temperature, was added with jO- and heated to "c" and stirred for 30 minutes. After cooling to room temperature, t00ml of ethyl acetate was added, and the mixture was transferred to a separatory funnel and washed with water. After washing with /N diluted hydrochloric acid, The oil layer was washed with water until it became transparent.The oil layer was washed with sulfuric acid) I
The desired coupler (
7) 3g of t-/ri was obtained. In the present invention, a known method such as the method described in US Pat. No. 2,322,027 can be used to introduce the compound of the present application and a coupler that can be used in combination into the silver halide emulsion layer. Examples include phthalic acid alkyl esters (dibutyl tucrate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citric acid esters (such as acetyl citric acid). tributyl), benzoic acid esters (e.g. octyl benzoate), alkyl amidic acid esters (e.g. dibutoxyethyl succinate,
diethyl azelate), 1-thumesic acid esters (e.g. tributyl trimesate), or boiling point of about 30°C
to 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone,
After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using polymers described in No. 3 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the photosensitive dye of the present invention, but other hydrophilic colloids can also be used alone or together with gelatin. . In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964). Examples of the hydrophilic colloids that can be used include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfate esters. Sugar derivatives such as cell 1 course derivatives, sodium alginate, # powder derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, boria-acrylamide 1-, polyvinyl There are a wide variety of synthetic hydrophilic polymeric materials such as imidazole, polyvinylpyrazole, etc., single or copolymers. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred are formal silver iodides containing from 2 mol % to 12 mol % silver iodide. The average grain size of silver halide grains in a photographic emulsion (grain diameter for spherical or near-spherical grains, edge length for cubic grains, expressed as an average calculated by the projected area). ) is not particularly limited, but is preferably 3μ or less. The grain size may be narrow or wide. Silver halide grains in photographic emulsions may have a regular crystal structure such as a cube or hexagonal, or may have a spherical or plate shape. It may have an irregular crystal form or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside one particle. Photographic emulsion used in the present invention, Glafkides
Written by Ch.i.m.i.e.t.
que Photographique (Paul M.
onte1, 1967), G, F, Duf
Written by f in Ph o t o graphic l
Emulsion Chemistry, (The
Focal Press, 1966), V.L.
Making and by Zelikman et al.
Coating Photographic Emu
lsion (The Focal PreSS, 1
964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which p and Ag in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called control F double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. After precipitation or physical ripening, emulsions are usually stripped of soluble salts, but this can be done by using the long-known Tardel water washing method, which involves gelling gelatin. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated seratin, etc.) A sedimentation method (floki, nylon) may also be used. Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example I (ed. Frlcser)
D'+e Grundlagender Photog
raphischen prozesse mit 5
ilber-halogcniden” (Akad
emischcVer Iagsgesellscha
ft, 1968) pages 675-734 can be used. Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (eg, stannous salts); Reduction sensitization method (amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds)
A noble metal sensitization method using complex salts of metals of the above group can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles, such as hendithiazolium salts, nitroimidazoles, nitrohesisimidazoles, chlorohenzimidazoles, promohenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, amino Triazoles, hencytriazoles, nitrohencytriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc.; mercapto-pyrimidines; mercaptotriazines; thioketo compounds, such as oxadolinthion; azaindenes , such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3;B7) tetraazaindenes), pentaazaindenes; hazenthiosulfonic acid, hazensulfin A number of compounds known as antifoggants or stabilizers can be added, such as acids, Hensensulfonic acid amides, and the like. The photographic emulsion layer or other hydrophilic colloid layer of the photosensitive dye made using the present invention may include coating aids, antistatic properties, sheerability improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization. For example, Zabonin (steroidal), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycolalkylamines or amides, polyethylene oxide adducts of silicone), glycyl derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Nonionic surfactants; alkyl carboxylates, alkyl sulfonates, alkyl hanzene sulfonates, alkylnafculene sulfonates, alkyl sulfates, alkyl phosphate esters, N-acyl-N-alkyl Carboxy groups such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino [74
, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides, and other amphoteric surfactants; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. In the photographic emulsion layer of the photographic light-sensitive material of the present invention, a cationic surfactant such as a heterocyclic quaternary ammonium salt and a phosphonium or sulfonium salt containing an aliphatic or heterocyclic ring can be used to increase sensitivity and increase contrast l-. , or for the purpose of accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones. etc. may also be included. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acryloni]-lyl, olefin, styrene, etc. alone or in combination, or together with these. Polymers containing a combination of acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. One example of photographic processing of a layer consisting of a photographic emulsion made using the present invention is Ebori No. - Chidis Closure No. 176 No. 2.
Any of the known methods and known treatment liquids as described on pages 8 to 30 can be used. The treatment temperature is usually selected between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. Color developers generally consist of alkaline water/8a containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N, N=-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino- N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-
amino-3-medyl-N-ethyl=N-β-methoxyethylaniline, etc.) can be used. In addition to this, there is a photo by F. A. Mason.
graphic processing chemist
ry (Focal Press, 1966)
226-229, U.S. Patent No. 2,193.015, No. 2
, No. 592.3'64, JP-A No. 4ill-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. It can also contain agents such as If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as Hensyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitors may also be added. A photographic emulsion layer after color development which may contain a coupler, a fogging agent such as sodium poron hydride, an auxiliary developer such as -phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, etc. are usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, compounds of polyvalent metals such as iron (■), cobalt (■), chromium (Vl), paulownia (IT), peracids, quinones,
Nitroso compounds and the like are used. For example, ferricyanide, dichromate, iron (III)
) or organic complex salts of cobalt (1'ff), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diI-lilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, or citric acid, tartaric acid, malic acid, etc. Complex salts of ta-acids; persulfates, permanganates; nitrosophenols, etc. can be used. Potassium ferricyanide, iron ethylenediaminetetraacetate (IIT
) Thorium and iron ethylenediaminetetraacetate <l11)
Ammonium is particularly useful. Ethylenediaminetetraacetic acid iron (■) complexes are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex norcyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazinone nucleus, deazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nucleus, etc.; Nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, sokuchi, indolenine nucleus, hens intrenine nucleus, indole nucleus, hens Oxidole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, henzimidazole nucleus, quinoline nucleus, etc. can be used. These nuclei may be substituted on carbon atoms. Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a diohydantoin nucleus, and a 2-thioxazolidine-2 nucleus as a nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiohalide. These sensitizing dyes may be used alone or in combination, and the silk combination of sensitizing color J- is often used especially for the purpose of supersensitization. Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing ring groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
．． 21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the same or other photographic emulsion layers or non-light-sensitive layers of the photographic light-sensitive materials prepared using the present invention, other dye-forming couplers, i.e., aromatic primary Even if a compound that can develop color by oxidative coupling with an amine developer (for example, a phenylene diamine derivative or an aminophenol derivative) is used, it will not be possible to use it. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloimidazole couplers, pyrazolopyrazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Examples of yellow couplers include acylacetamide couplers (eg, hendiylacetanilide, pivaloylacetanilide), and examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to DIR couplers, there are also colorless DIR couplers in which the product of the camping reaction is colorless and releases a development inhibitor.
It may also contain a campling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added to two or more different layers. Of course it doesn't matter. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioquinone, etc.), activated vinyl compounds (1,3,5-triacryloyl-hexahyto”rho S-triazine,
1.3-vinylsulfonyl-2-propatol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-5-1-riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photographic material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, hensitriazole compounds substituted with an oryl group (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., U.S. Pat. Nos. 3,314,794 and 3,352°) 681), hensifenone compounds (for example, those described in JP-A-46-2784)
, cinnamate ester compounds (e.g. U.S. Pat. No. 3,705)
．． No. 805, those described in No. 3,707,375),
Butadiene compounds (e.g. U.S. Pat. No. 4,045,229)
(as described in US Pat. No. 3,700,455) or benzoxidol compounds (such as those described in US Pat. No. 3,700,455). UV-absorbing couplers (e.g. α-naphthol cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. These ultraviolet absorbers may be mordanted in specific layers. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, sudyryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination with 2M or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. Example 7 A multilayer color photosensitive material sample having each layer having the composition shown below was prepared on a cellulose triacetate film support. 11th@; antihalation layer black gelatin layer containing colloidal silver λ layer; intermediate layer 2, emulsified dispersion of tertiary-t-octylhydroquinone Kanakura gelatin layer 3rd H@H first red-sensitive emulsion layer silver iodobromide Emulsion (silver iodide; 5 mol%)...
・・・・・・Silver coating amount /, A9/m” Sensitizing dye I・・・・・・・・・μ for 1 mole of silver,
jX 10-4 mol sensitizing dye■・・・・・・・・・・・・i for 1 mol of silver, jxio 2 4 mol coupler EX-/・・・・・・・・・・・・ 1 mol of silver Coupler EX-J: 0.003 mol per mol of silver μth layer; Second red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol%)・・・・・・・・・
...Silver coating amount /4' g/m2 Sensitizing dye 1...3 x 10-4 mol sensitizing dye per 1 mol silver■...・・・・・・For 1 mole of silver/×
10-4 mole coupler EX-/・・・・・・・・・0.00.2 mole coupler EX-2 for 1 mole of silver 0.02 mole coupler EX-3...O, ooit mole j# for 1 mole of silver; 61st mole same as intermediate layer 21st; 1st green-sensitive emulsion 1 - Silver iodobromide emulsion (silver iodide; 4 mol%)...
...Silver coating amount /, jl/m2 Sensitizing dye ■ ... ... ... ... For 1 mole of silver! r o, or molar coupler EX-t for 1 mole of silver o, oor molar coupler EX-2 for 1 mole of silver 0.00 per mole! Mole No. 7: Second green-sensitive emulsion layer silver iodobromide emulsion (silver iodide; 4 mol%)...
・・・・・・Amount of silver coating / , 3,! 9/yl
``Sensitizing dye■・・・・・・・・・3X10-4 moles per 1 mole of silver Sensitizing dye■・・・・・・・・・I per 1 mole of silver , zxio 4 mole coupler EX-7...00017 moles per mole of silver Coupler EX-1...0. 003 mol layer; yellow filter layer with yellow colloidal silver and λ, 1-G-1 in gelatin aqueous solution
- gelatin layer containing an emulsified dispersion of octylhydroquinone Second layer; first emulsion layer silver iodobromide emulsion (silver iodide; 4 mol %)...
... Silver coating amount θ, 7.17/mz Coupler EX-1r... θ, +2 for 1 mole of silver! Mol coupler EX-ta...0.0121 mol per 1 mol of silver; io layer; first blue-sensitive emulsion layer silver iodobromide (silver iodide; 4 mol %)・・・・・・Amount of silver coating
0. lr97m" Coupler EX-1r・・・・・・O, O6 mol per mol of silver 11th layer; 1st protective layer ' Silver iodobromide (silver iodide 1 mol%, average Particle size 0.07μ)...
・・・・・・・・・Amount of silver coating 0-! 12th gelatin layer containing fi/m2 ultraviolet absorber UV absorber; λth protective layer gelatin layer containing polymethylmethanoacrylate particles (diameter approximately l.j/Z). In addition to the above composition, gelatin hardening agent H-7 and a surfactant were added to each 1-. The sample prepared as described above was designated as sample 101. Preparation of Samples 10/10/10 Samples 10/10/10 were prepared in the same manner as Sample 10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10/10. A sample of 1ol-ito was wedge exposed to sunlight,
After processing as described below, a product with almost the same sensitivity and gradation was obtained. The sharpness of the green sensitive layer of these samples was measured using the conventional MT method.
Evaluation was made using the F value. Chemical coupler used to make the sample EX-/ EX-2 EX-J EX-μ Molecular molecule Approximately 000 EX-j EX-A EX-7 EX-t EX-2 H-/ CH2=CH-802 -CH2-CONH-CH2CH
2=CH-8O2-CH2-CONH-CH2UV-/ Sensitizing dye■ (CH2) 3sO3H-N((,:2H5)3#I!
Sensitizing dye ■ Sensitizing dye ■ 2H5 Used in the present invention, 7? - The chemical structure of the comparative compound is then EX-/+17 Ha・・・・・・・・・・・・・・・
...3 minutes/j seconds, ..., ..., ...
...6 minutes 30 seconds, 2 bleaching...
・・・3 Washing with water・・・・・・・・・・・・・・・・・・
・・・・・・・・・3 minutes is Sho≠ Fixed・・・・・・
・・・・・・・・・・・・・・・4 minutes and 30 seconds!
Washing with water・・・・・・・・・・・・・・・・・・・・・・・・
3 minutes is seconds t Stable・・・・・・・・・・・・・・・・・・
3 minutes/Nrj; The composition of the treatment liquid used in each step is the same as that of the lower U. Color liquid sodium nitrilotriacetate 11um 1. og sodium sulfite μ, og sodium carbonate 3o, 09 bromidating power))/. ≠l Hydroxylamine sulfate J Tomiko, 4Lyhiro-(N-ethyl-N-β-hydroxyethylamino)-twomethyl 7211 sulfate p,! Add water! Bleach solution ammonium bromide tt, 0.09 -r -7 water (23%), l 3 , Occ ethylene'diamine-tetraacetic acid butynato 11um iron salt i 3o, o
g ice the, itt-, oct. Add water ll Titration solution Tetra y) 5 lysine phosphoric acid 1) Rum 2. OoC sodium sulfite g, og No. 3 ammonium sulfate (70%)/7j, OCC sodium bisulfite ≠. 6! j Add water and add ' 4 Stable solution Ho#, -tII 7 g, Occ Add water and 'l About the obtained sample / mrrLi-! MTFI direct 01 direct placement 11 feet of green 1 layer of book and VO book. The results are shown in Table 1. From Table 1, it can be seen that the MTF value of the coupler using the coupler of the present application is significantly higher than that of the conventional DIR coupler using gold. The effects of the invention of this application are obvious. Example 2 A multilayer color photosensitive material sample was prepared on a polyethylene terephthalate film support, each layer having the composition shown below. 1st layer; no-ration prevention layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer J,! Gelatin layer containing an emulsified dispersion of ctylno-ito-roquinone Third layer 1 Red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 7 mol %)
・・・・・・Amount of chain wheel cloth λ, 09/m” Sensitizing dye I・・・・・・・・・・・・Bxlo mole per mole of silver Sensitizing dye■・・・・・・・・・・・・・・・For 91 mol / , ! ... Old... 0.003 mole per mole of silver Coupler EX-ta ...... 0.00 mole per mole of silver tricresyl phosphate・・0-3!j/m2 Dibutyl phthalate・・・・・・・・・・・・0.
2ji/, 2 first layer; first holding layer silver iodobromide (silver iodide 1 molti, average grain size 0.07n)...
...... Silver coating amount 0.197 m2 Gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-/1st layer: 1st protective layer Polymethylmethanoacrylate particles (diameter approx. l.jll) Apply a layer of gelatin containing i. In addition to the above composition, gelatin hardener H-7 and a surfactant were added to each layer. The sample prepared as described above was designated as sample iii. Preparation of samples //2 to //2 Samples were prepared in the same manner as sample /// except that the coupler used in place of the EX-ta used in sample /// was changed as shown in Table (2). Compound EX-/2 used to prepare the sample EX-/2 and the other compounds except for the coupler of the present invention were the same as in Example (1). When samples (///) to (//ri) were wedge-exposed with white light and subjected to the same processing as in Example (1), almost the same sensitivity gradation was obtained. For these samples, the MTF values of μ books and po books per MIT were measured. The results are shown in Table 1. From the table, it can be seen that the MTF value is significantly higher when using the coupler of the present invention than when using a normal DIR coupler. The effects of the invention of this application are obvious. Example 3 To test the storage stability of the film used in Example-2, samples (//3) to (/14) were kept at room temperature for 3 days. ≠j'c-10 After storage for 3 days, wedge exposure was performed with white light, the following treatment was performed, and sensitometry was performed. The results are shown in Table 3. The processing used here was as follows: F) (C20'C). 1. Development...
・・・70 minutes 2 stop・・・・・・・・・・・・
・・・・・・・・・・・・・・・1 minute 3 fixing・・・・
・・・・・・・・・・・・・・・・・・・・・1 minute 4 washes・・・・・・・・・・・・・・・・・・・
...10 minutes The processing liquid composition used in each step will be returned in the notification below. From Table 3, the coupler of the present invention has a hydrolysis rate of 19'L during storage.
No deterioration in sensitivity is observed because development inhibitors are not released due to the above reasons. The effects of the invention of this application are obvious. Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 13 [] 7th month of 2015 To the Commissioner of the Japan Patent Office' 1. Indication of the case 1939 Showa Jt9 Patent Application No. 10/>2.2
No. 3 No. 2. Title of the invention: Silver chloride color photographic A photosensitive material 3. Relationship with the person making the amendment case Patent applicant Location: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Minoru Ohnishi, Representative of Fuji Photo Film Co., Ltd.
゛・ ] 4. Subject of amendment: 1. Detailed explanation of the invention in the specification. #5. Contents of amendment The statement in the column of ``Detailed explanation of the invention'' in the specification shall be amended as follows. Insert the following statement after the first line of page 27. Among the cases where r PU G and any one of Xl, X2, X3, and Xi become a divalent group to form a ring structure, this is a preferable case of the following structure. X 2 Together with this, the entire ring structure is formed. ”

Claims (1)

[Scope of Claims] A silver halide color photographic material containing a compound that can cleave a group represented by the following general formula by reaction with an oxidized developing agent. Represents the general formula -N-, XI, X2, X3, X4 and
5 represents a hydrogen atom or an organic residue, PUG represents a photographically useful group, n represents 1 or 2, Xl, X
Any two of 2, X3, x4, x5 and PUG may be connected as a divalent group to form a ring structure. When n is 2, two 2.2 X and two X4 may be the same or different.